Use of sulfonyloxadiazolones as microbicides

ABSTRACT

Sulphonyloxadiazolones of the formula ##STR1## in which A represents a single bond or represents alkanediyl, alkenediyl, alkinediyl or a grouping --*O--CH 2  --, --*O--CH 2  --CH 2  --, --*CH 2  --O--, --*CH 2  --O--CH 2  --CH 2  --, --*CH 2  --S--, --*S--CH 2  --, ##STR2## or ##STR3## where the atom labelled by * is in each case attached to R 1  and 
     R 3  represents hydrogen or alkyl, 
     R 1  represents hydrogen, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted aryl or optionally substituted heterocyclyl and 
     R 2  represents in each case optionally substituted alkyl, alkenyl, dialkylamino, aryl or heterocyclyl, 
     are highly suitable for controlling undesirable microorganisms in crop protection and in the protection of materials. 
     Novel sulphonyloxadiazolones of the formula ##STR4## in which A and R 1  are as defined above and 
     R 4  represents optionally substituted alkyl, optionally substituted alkenyl, dialkylamino, nitro-substituted phenyl which may also contain one or two further substituents, or represents optionally substituted heterocyclyl, but where R 4  does not represent propyl if A represents a direct bond and R 1  represents 2,4,5-trimethyl-phenyl, 
     and a process for preparing these substances.

The present invention relates to the use of sulphonyloxadiazolones, someof which are known, as microbicides in crop protection and in theprotection of materials. Moreover, the invention also relates to novelsulphonyloxadiazolones and to a process for their preparation.

Certain sulphonyloxadiazolones, such as, for example,4-[(4-chlorophenyl)-sulphonyl]-3-(2,4,6-trimethylphenyl)-1,2,4-oxadiazol-5(4H)-one,are already known (cf. Zh. Org. Khim. 27 (1991), 1262-1270). However, abiological action of these compounds has hitherto not been described.

It has now been found that sulphonyloxadiazolones of the formula##STR5## in which A represents a single bond or represents alkanediyl,alkenediyl, alkinediyl or a grouping --*O--CH₂ --, --*O--CH₂ --CH₂ --,--*CH₂ --O--, --*CH₂ --O--CH₂ --CH₂ --, --*CH₂ S--, --*S--CH₂ --,##STR6## or ##STR7## where the atom labelled by * is in each caseattached to R¹ and

R³ represents hydrogen or alkyl,

R¹ represents hydrogen, optionally substituted cycloalkyl, optionallysubstituted cycloalkenyl, optionally substituted aryl or optionallysubstituted heterocyclyl and

R² represents in each case optionally substituted alkyl, alkenyl,dialkylamino, aryl or heterocyclyl,

are highly suitable for controlling undesirable microorganisms in cropprotection and in the protection of materials.

Surprisingly, the sulphonyloxadiazolones of the formula (I) to be usedaccording to the invention show considerably better activity againstundesirable microorganisms, in particular fungi, than theconstitutionally most similar prior-art substances of the same directionof action.

The formula (I) provides a general definition of the substances to beused according to the invention.

Heterocyclyl represents cyclic compounds in which at least one ringmember is a heteroatom, i.e. an atom different from carbon. If the ringcontains a plurality of heteroatoms, these can be identical ordifferent. Preferred heteroatoms are oxygen, nitrogen or sulphur. If thering contains a plurality of oxygen atoms, these are not adjacent.

A preferably represents a single bond or represents alkanediyl having 1to 4 carbon atoms, alkenediyl having 2 to 4 carbon atoms, alkinediylhaving 2 to 4 carbon atoms or a grouping --*O--CH₂ --, --*O--CH₂ --CH₂--, --*CH₂ --O--, --*CH₂ --O--CH₂ --CH₂ --, --*CH₂ --S--, --*S--CH₂ --,##STR8## or ##STR9## where the atom labelled by * is in each caseattached to R¹. R³ preferably represents hydrogen or alkyl having 1 to 4carbon atoms.

R¹ preferably represents hydrogen, or represents cycloalkyl having 3 to8 carbon atoms or cycloalkenyl having 3 to 8 carbon atoms, each of whichis optionally mono- to trisubstituted by identical or differentsubstituents from the group consisting of halogen and alkyl having 1 to3 carbon atoms.

R¹ furthermore preferably represents aryl having 6 to 10 carbon atoms,where each of these radicals may be mono- to trisubstituted by identicalor different substituents from the group consisting of

halogen, nitro, carbamoyl;

in each case straight-chain or branched alkyl, alkoxy, alkylthio oralkylsulphonyl having in each case 1 to 6 carbon atoms;

in each case straight-chain or branched alkenyl or alkenyloxy having ineach case 2 to 6 carbon atoms;

in each case straight-chain or branched halogenoalkyl, halogenoalkoxy,halogenoalkylthio or halogenoalkylsulphonyl having in each case 1 to 6carbon atoms and 1 to 5 identical or different halogen atoms;

in each case straight-chain or branched halogenoalkenyl orhalogenoalkenyloxy having in each case 2 to 6 carbon atoms and 1 to 5identical or different halogen atoms;

in each case straight-chain or branched alkylamino, dialkylamino,alkylcarbonyl, alkoxycarbonyl, hydroximinoalkyl or alkoximinoalkylhaving in each case 1 to 6 carbon atoms in the individual alkylmoieties;

in each case doubly attached alkylene or dioxyalkylene having in eachcase 1 to 6 carbon atoms and being in each case optionally mono- totetrasubstituted by identical or different substituents from the groupconsisting of halogen, straight-chain or branched alkyl having from 1 to4 carbon atoms and straight-chain or branched halogenoalkyl having 1 to4 carbon atoms and 1 to 5 identical or different halogen atoms;

cycloalkyl having 3 to 6 carbon atoms;

and

aryl, aryloxy, arylthio, arylalkyl, arylalkyloxy, arylalkylthio,heterocyclyl, heterocyclyloxy, heterocyclylthio, heterocyclylalkyl,heterocyclylalkyloxy or heterocyclylalkylthio, where these aromatic orheterocyclic radicals may be mono- to trisubstituted by identical ordifferent substituents from the group consisting of

halogen, nitro, straight-chain or branched alkyl having 1 to 4 carbonatoms,

straight-chain or branched halogenoalkyl having 1 to 4 carbon atoms and1 to 5 identical or different halogen atoms,

straight-chain or branched alkoxy or alkylthio having 1 to 4 carbonatoms,

and straight-chain or branched halogenoalkoxy having 1 to 4 carbon atomsand 1 to 9 identical or different halogen atoms.

R¹ moreover preferably represents represents an unsaturated heterocyclylradical having 5 or 6 ring members and 1 to 3 heteroatoms which mayoptionally be mono- to trisubstituted by identical or differentsubstituents from the group consisting of

halogen, nitro, amino, hydroxyl;

in each case straight-chain or branched alkyl, alkoxy, alkylthio oralkylsulphonyl having in each case 1 to 6 carbon atoms;

in each case straight-chain or branched alkenyl or alkenyloxy having ineach case 2 to 6 carbon atoms;

in each case straight-chain or branched halogenoalkyl, halogenoalkoxy,halogenoalkylthio or halogenoalkylsulphonyl having in each case 1 to 6carbon atoms and 1 to 13 identical or different halogen atoms;

in each case straight-chain or branched alkylamino, dialkylamino,alkylcarbonyl, alkoxycarbonyl, hydroximinoalkyl or alkoximinoalkylhaving in each case 1 to 6 carbon atoms in the individual alkyl moiety;

cycloalkyl having 3 to 6 carbon atoms;

and

aryl, aryloxy, arylthio, arylalkyl, arylalkyloxy, arylalkylthio,heterocyclyl, heterocyclyloxy, heterocyclylthio, heterocyclylalkyl,heterocyclylalkyloxy or heterocyclylalkylthio, where these aromatic orheterocyclic radicals may be mono- to trisubstituted by identical ordifferent substitutents from the group consisting of

halogen, nitro, straight-chain or branched alkyl having 1 to 4 carbonatoms, straight-chain or branched halogenoalkyl having 1 to 4 carbonatoms and 1 to 9 identical or different halogen atoms,

straight-chain or branched alkoxy or alkylthio having 1 to 4 carbonatoms, straight-chain or branched halogenoalkoxy or halogenoalkylthiohaving 1 to 4 carbon atoms and 1 to 9 identical or different halogenatoms.

R² preferably represents alkyl having 1 to 4 carbon atoms, alkenylhaving 2 to 4 carbon atoms, halogenoalkyl having in each case 1 to 4carbon atoms and 1 to 5 identical or different halogen atoms,halogenoalkenyl having in each case 2 to 4 carbon atoms and 1 to 5identical or different halogen atoms or represents dialkylamino havingin each case 1 to 4 carbon atoms in the two alkyl groups.

R² moreover preferably represents aryl having 6 to 10 carbon atoms whichmay be mono- to trisubstituted by identical or different substituentsfrom the group consisting of nitro, halogen, alkyl having 1 to 4 carbonatoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbonatoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 identical ordifferent halogen atoms, halogenoalkoxy having 1 to 4 carbon atoms and 1to 5 identical or different halogen atoms and halogenoalkylthio having 1to 4 carbon atoms and 1 to 5 identical or different halogen atoms.

R² furthermore preferably represents a heterocyclyl radical having 5 or6 ring members and 1 to 3 heteroatoms, such as nitrogen, oxygen andsulphur, where this radical may contain an oxo group and may be mono- totrisubstituted by identical or different substituents from the groupconsisting of halogen, cyano, nitro, amino, hydroxyl, alkyl having 1 to4 carbon atoms, alkoxy having 1 to 4 carbon atoms, halogenoalkyl having1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms,halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 identical ordifferent halogen atoms, alkylcarbonyl having 1 to 4 carbon atoms in thealkyl moiety, alkoxycarbonyl having 1 to 3 carbon atoms in the alkoxymoiety, carbamoyl, alkylaminocarbonyl having 1 to 4 carbon atoms in thealkyl moiety, dialkylaminocarbonyl having 1 to 4 carbon atoms in theindividual alkyl moieties, hydroximinoalkyl or alkoximinoalkyl having ineach case 1 to 4 carbon atoms in the individual alkyl moieties andcycloalkyl having 3 to 6 carbon atoms.

A particularly preferably represents a single bond or representsmethanediyl, 1,1-ethanediyl, 1,2-ethanediyl 1,1-, 1,2-, 1,3- or2,2-propanediyl, 1,1-, 1,2-, 1,3-, 1,4-, 2,2-, 2,3-butanediyl, 1,1-,1,2- or 1,3-(2-methyl-propanediyl), 1,1-ethenediyl, 1,2-ethenediyl 1,1-,1,2- or 1,3-propenediyl, ethinediyl, 1,3-propinediyl or a grouping--*O--CH₂ --, --*O--CH₂ --CH₂ --, --*CH₂ --O--, --*CH₂ --O--CH₂ --CH₂--, --*CH₂ --S--, --*S--CH₂ --, ##STR10## or ##STR11## where the atomlabelled by * is in each case attached to R¹. R³ particularly preferablyrepresents hydrogen or methyl.

R¹ particularly preferably represents hydrogen, or representscyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentenyl orcyclohexenyl, each of which is optionally mono- to trisubstituted bychlorine, methyl, ethyl, n- or i-propyl.

R¹ moreover particularly preferably represents phenyl which may be mono-to trisubstituted by identical or different substituents from the groupconsisting of fluorine, chlorine, bromine, nitro, carbamoyl, methyl,ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- ori-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulphonyl orethylsulphonyl, trifluoromethyl, trifluoroethyl, difluoromethoxy,trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy,difluoromethylthio, difluorochloromethylthio, trifluoromethylthio ortrifluoromethylsulphonyl, methylamino, ethylamino, n- or i-propylaminodimethylamino, diethylamino, acetyl, propionyl, methoxycarbonyl,ethoxycarbonyl, hydroximinomethyl, hydroximinoethyl, methoximinomethyl,ethoximinomethyl, methoximinoethyl and ethoximinoethyl,

in each case doubly attached trimethylene (propane-1,3-diyl),methylenedioxy or ethylenedioxy, which is optionally mono- totetrasubstituted by identical or different substituents from the groupconsisting of fluorine, chlorine, methyl and trifluoromethyl,

cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl,

and/or

by phenyl, phenoxy, phenylthio, benzyl, benzyloxy, benzylthio, pyridyl,pyrimidinyl or thienyl, where these radicals may be mono- totrisubstituted by identical or different substituents from the groupconsisting of fluorine, chlorine, bromine, nitro, methyl, ethyl, n- ori-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy,methylthio, ethylthio, n- or i-propylthio, trifluoromethyl,trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxyand trifluoroethoxy.

R¹ furthermore particularly preferably represents thienyl, furyl orpyridyl, where these radicals may be mono- to trisubstituted byidentical or different substituents from the group consisting offluorine, chlorine, bromine, nitro, amino, hydroxyl, methyl, ethyl, n-or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy,methylthio, ethylthio, n- or i-propylthio, methylsulphonyl orethylsulphonyl, trifluoromethyl, trifluoroethyl, difluoromethoxy,trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy,difluoromethylthio, difluorochloromethylthio, trifluoromethylthio ortrifluoromethylsulphonyl, methylamino, ethylamino, n- or i-propylamino,dimethylamino, diethylamino, acetyl, propionyl, methoxycarbonyl,ethoxycarbonyl, hydroximinomethyl, hydroximinoethyl, methoximinomethyl,ethoximinomethyl, methoximinoethyl or ethoximinoethyl, cyclopropyl,cyclobutyl, cyclopentyl and cyclohexyl,

and/or by

phenyl, phenoxy, phenylthio, benzyl, benzyloxy and/or benzylthio, wherethese aromatic radicals may be mono- to trisubstituted by identical ordifferent substituents from the group consisting of fluorine, chlorine,bromine, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- ori-propylthio, trifluoromethyl, trifluoroethyl, difluoromethoxy,trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy,difluoromethylthio, difluorochloromethylthio and trifluoromethylthio.

R² particularly preferably represents methyl, ethyl, n- or i-propyl, n-,i-, s-, or t-butyl, dimethylamino or diethylamino.

R² moreover particularly preferably represents phenyl which may be mono-to trisubstituted by identical or different substituents from the groupconsisting of fluorine, chlorine, bromine, nitro, methyl, ethyl,methoxy, ethoxy, methylthio, ethylthio, trifluoromethyl, trifluoroethyl,difluoromethoxy, trifluoromethoxy, difluorochloromethoxy,trifluoroethoxy, difluoromethylthio, difluorochloromethylthio andtrifluoromethylthio.

R² furthermore particularly preferably represents furyl, thienyl,oxazolyl, isoxazolyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl,oxadiazolyl, thiadiazolyl, pyridinyl, pyridazinyl, pyrazinyl,1,2,3-triazinyl, 1,2,4-triazinyl, 1,3,5-triazinyl, 1,2,4-triazolonyl,pyrrolidinyl, piperidinyl or morpholinyl, where these radicals may bemono-, di- or trisubstituted by identical or different substituents fromthe group consisting of fluorine, chlorine, bromine, cyano, nitro,amino, hydroxyl, carbamoyl, methyl, ethyl, n- or i-propyl, n-, i-, s-,or t-butyl, cyclopropyl, methoxy, ethoxy, n- or i-propoxy,trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy,acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, hydroxyiminomethyl,hydroxyiminoethyl, methoxyiminomethyl, ethoxyiminomethyl,methoxyiminoethyl and ethoxyiminoethyl.

A very particularly preferably represents a single bond or representsmethanediyl, 1,1-ethanediyl, 1,2-ethanediyl 1,1-, 1,2-, 1,3- or2,2-propanediyl, 1,1-, 1,2-, 1,3-, 1,4-, 2,2-, 2,3-butanediyl, 1,1-,1,2- or 1,3-(2-methyl-propanediyl), 1,2-ethenediyl, ##STR12## --*O--CH₂--CH₂ --, --*CH₂ --O--, --*CH₂ --O--CH₂ --CH₂ --, --*S--CH₂ --, --*CH₂--S-- or ##STR13## where the atom labelled by * is in each case attachedto R¹. R¹ very particularly preferably represents hydrogen orcyclohexenyl.

R¹ moreover very particularly preferably represents phenyl which isoptionally mono- or disubstituted by fluorine, chlorine, bromine,methyl, ethyl, methoxy, nitro, trifluoromethyl, trifluoromethoxy, phenyland/or phenoxy.

R¹ moreover very particularly preferably represents a radical of theformula ##STR14## R¹ furthermore very particularly preferably representsthienyl, furyl or pyridyl.

R² very particularly preferably represents methyl, ethyl, n- ori-propyl, n-, i-, s-, or t-butyl, dimethylamino or diethylamino.

R² moreover very particularly preferably represents phenyl which isoptionally mono- or disubstituted by fluorine, chlorine, bromine, nitro,methyl, ethyl and/or methoxy.

R² furthermore very particularly preferably represents furyl, thienyl,isoxazolyl, pyrazolyl, thiazolyl, imidazolyl, pyridyl or1,2,4-triazolonyl which is optionally mono-, di- or trisubstituted bychlorine, bromine, amino, hydroxyl, methyl and/or cyclopropyl.

R² furthermore very particularly preferably represents pyrrolidinyl,piperidinyl or morpholinyl.

Some of the sulphonyloxadiazolones of the formula (I) which can be usedaccording to the invention are known (cf. Zh. Org. Khim. 27 (1991),1262-1270).

The sulphonyloxadiazolones of the formula ##STR15## in which Arepresents a single bond or represents alkanediyl, alkenediyl,alkinediyl or a grouping --*O--CH₂ --, --*O--CH₂ --CH₂ --, --*CH₂ --O--,--*CH₂ --O--CH₂ --CH₂ --, --*CH₂ --S--, --*S--CH₂ --, ##STR16## or##STR17## where the atom labelled by * is in each case attached to R¹and R³ represents hydrogen or alkyl,

R¹ represents hydrogen, optionally substituted cycloalkyl, optionallysubstituted cycloalkenyl, optionally substituted aryl or optionallysubstituted heterocyclyl and

R⁴ represents optionally substituted alkyl, optionally substitutedalkenyl, dialkylamino, nitro-substituted phenyl which may also containone or two further substituents, or represents optionally substitutedheterocyclyl, but where R⁴ does not represent propyl if A represents adirect bond and R¹ represents 2,4,6-trimethylphenyl

are novel.

The sulphonyloxadiazolones of the formula (Ia) can be prepared byreacting oxadiazolones of the formula ##STR18## in which A and R¹ areeach as defined above, with sulphonyl halides of the formula

    R.sup.4 --SO.sub.2 --X                                     (III)

in which

R⁴ is as defined above and

X represents halogen,

if appropriate in the presence of an acid binder and if appropriate inthe presence of a diluent.

The other compounds of the formula (I) can be prepared in the samemanner.

The formula (Ia) provides a general definition of the novelsulphonyloxadiazolones. In this formula, A and R¹ each preferably havethose meanings which have already been mentioned as being preferred forthese radicals in connection with the description of thesulphonyloxadiazolones of the formula (I).

R⁴ preferably represents alkyl having 1 to 4 carbon atoms, alkenylhaving 2 to 4 carbon atoms, halogenoalkyl having in each case 1 to 4carbon atoms and 1 to 5 identical or different halogen atoms,halogenoalkenyl having in each case 2 to 4 carbon atoms and 1 to 5identical or different halogen atoms or represents dialkylamino havingin each case 1 to 4 carbon atoms in the two alkyl groups, but where R⁴does not represent propyl if A represents a direct bond and R¹represents 2,4,6-trimethyl-phenyl.

R⁴ moreover preferably represents nitro-substituted phenyl which mayadditionally be mono- or disubstituted by identical or differentsubstituents from the group consisting of nitro, halogen, alkyl having 1to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5identical or different halogen atoms, halogenoalkoxy having 1 to 4carbon atoms and 1 to 5 identical or different halogen atoms andhalogenoalkylthio having 1 to 4 carbon atoms and 1 to 5 identical ordifferent halogen atoms.

R⁴ furthermore preferably represents a heterocyclyl radical having 5 or6 ring members and 1 to 3 heteroatoms, such as nitrogen, oxygen and/orsulphur, where this radical may contain an oxo group and may be mono- totrisubstituted by identical or different substituents from the groupconsisting of halogen, cyano, nitro, amino, hydroxyl, alkyl having 1 to4 carbon atoms, alkoxy having 1 to 4 carbon atoms, halogenoalkyl having1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms,halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 identical ordifferent halogen atoms, alkylcarbonyl having 1 to 4 carbon atoms in thealkyl moiety, alkoxycarbonyl having 1 to 3 carbon atoms in the alkoxymoiety, carbamoyl, alkylaminocarbonyl having 1 to 4 carbon atoms in thealkyl moiety, dialkylaminocarbonyl having 1 to 4 carbon atoms in theindividual alkyl moieties, hydroximinoalkyl or alkoximinoalkyl having ineach case 1 to 4 carbon atoms in the individual alkyl moieties andcycloalkyl having 3 to 6 carbon atoms.

In the formula (Ia), A and R¹ particularly preferably represent thoseradicals which have already been mentioned as being particularlypreferred for these radicals in connection with the description of thesulphonyloxadiazolones of the formula (Ia).

R⁴ particularly preferably represents methyl, ethyl, n- or i-propyl, n-,i-, s-, or t-butyl, dimethylamino or diethylamino, but where R⁴ does notrepresent n- or i-propyl if A represents a direct bond and R¹ represents2,4,6-trimethylphenyl.

R⁴ moreover particularly preferably represents nitro-substituted phenylwhich may additionally be mono- or disubstituted by identical ordifferent substituents from the group consisting of fluorine, chlorine,bromine, nitro, methyl, ethyl, methoxy, ethoxy, methylthio, ethylthio,trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy,difluorochloromethoxy, trifluoroethoxy, difluoromethylthio,difluorochloromethylthio and trifluoromethylthio.

R⁴ furthermore particularly preferably represents furyl, thienyl,oxazolyl, isoxazolyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl,oxadiazolyl, thiadiazolyl, pyridinyl, pyridazinyl, pyrazinyl,1,2,3-triazinyl, 1,2,4-triazinyl, 1,3,5-triazinyl, 1,2,4-triazolonyl,pyrrolidinyl, piperidinyl or morpholinyl, where these radicals may bemono-, di- or trisubstituted by identical or different substituents fromthe group consisting of fluorine, chlorine, bromine, cyano, nitro,amino, hydroxyl, carbamoyl, methyl, ethyl, n- or i-propyl, n-, i-, s-,or t-butyl, cyclopropyl, methoxy, ethoxy, n- or i-propoxy,trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy,acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, hydroxyiminomethyl,hydroxyiminoethyl, methoxyiminomethyl, ethoxyiminomethyl,methoxyiminoethyl and ethoxyiminoethyl.

In the formula (Ia), A and R¹ each very particularly preferablyrepresent those radicals which have already been mentioned as being veryparticularly preferred for these radicals in connection with thedescription of the sulphonyloxadiazolones of the formula (Ia).

R⁴ very particularly preferably represents methyl, ethyl, n- ori-propyl, n-, i-, s-, or t-butyl, dimethylamino or diethylamino, butwhere R⁴ does not represent n- or i-propyl if A represents a direct bondand R¹ represents 2,4,6-trimethylphenyl.

R⁴ moreover very particularly preferably represents nitro-substitutedphenyl which may additionally be substituted by fluorine, chlorine,bromine, nitro, methyl, ethyl or methoxy.

R⁴ furthermore very particularly preferably represents furyl, thienyl,isoxazolyl, pyrazolyl. thiazolyl, imidazolyl, pyridyl or1,2,4-triazolonyl, which is optionally mono-, di- or trisubstituted bychlorine, bromine, amino, hydroxyl, methyl and/or cyclopropyl.

R⁴ furthermore very particularly preferably represents pyrrolidinyl,piperidinyl or morpholinyl.

Examples of substances according to the invention which may be mentionedare the sulphonyloxadiazolones listed in the tables below:

                  TABLE 1                                                         ______________________________________                                         ##STR19##                    (I-b)                                           ______________________________________                                    

where R⁴ represents the following substituents: ##STR20##

                  TABLE 2                                                         ______________________________________                                                                      (I-c)                                           ______________________________________                                         where R.sup.4 represents the substituents mentioned in Table 1.

                  TABLE 3                                                         ______________________________________                                         ##STR21##                    (I-d)                                           ______________________________________                                    

where R⁴ represents the substituents mentioned in Table 1.

                  TABLE 4                                                         ______________________________________                                         ##STR22##                    (I-e)                                           ______________________________________                                    

where R⁴ represents the substituents mentioned in Table 1.

                  TABLE 5                                                         ______________________________________                                         ##STR23##                    (I-f)                                           ______________________________________                                    

where R⁴ represents the substituents mentioned in Table 1.

                  TABLE 6                                                         ______________________________________                                         ##STR24##                    (I-g)                                           ______________________________________                                    

where R⁴ represents the substituents mentioned in Table 1.

                  TABLE 7                                                         ______________________________________                                         ##STR25##                    (I-h)                                           ______________________________________                                    

where R⁴ represents the substituents mentioned in Table 1.

                  TABLE 8                                                         ______________________________________                                         ##STR26##                    (I-i)                                           ______________________________________                                    

where R⁴ represents the substituents mentioned in Table 1.

                  TABLE 9                                                         ______________________________________                                         ##STR27##                    (I-j)                                           ______________________________________                                    

where R⁴ represents the substituents mentioned in Table 1.

                  TABLE 10                                                        ______________________________________                                         ##STR28##                    (I-k)                                           ______________________________________                                    

where R⁴ represents the substituents mentioned in Table 1.

                  TABLE 11                                                        ______________________________________                                         ##STR29##                    (I-l)                                           ______________________________________                                    

where R⁴ represents the substituents mentioned in Table 1.

                  TABLE 12                                                        ______________________________________                                         ##STR30##                    (I-m)                                           ______________________________________                                    

where R⁴ represents the substituents mentioned in Table 1.

                  TABLE 13                                                        ______________________________________                                         ##STR31##                    (I-n)                                           ______________________________________                                    

where R⁴ represents the substituents mentioned in Table 1.

Using, for example, 3-phenyl-4H-[1,2,4]oxadiazol-5-one and3,5-dimethyl-isoxazole-4-sulphonyl chloride as starting materials, thecourse of the process according to the invention can be illustrated bythe following scheme: ##STR32##

The formula (II) provides a general definition of the oxadiazolonesrequired as starting materials for carrying out the process according tothe invention. In this formula, A and R¹ preferably or particularlypreferably have those meanings which have already been mentioned inconnection with the description of the compounds of the formula (I)according to the invention as being preferred or as being particularlypreferred for A and R¹.

The oxadiazolones of the formula (II) are known or can be prepared byknown methods (cf. Synthesis 6, (1983), 483-486; J. Heterocyclic Chem.10, (1973), 357-362; J. Org. Chem. 41, (1976), 3233; J. HeterocyclicChem. 30 (5), (1993), 1253-1260).

The formula (III) provides a general definition of the sulphonyl halidesfurthermore required as reaction components for carrying out the processaccording to the invention. In this formula (III), R⁴ preferably orparticularly preferably has that meaning which has already beenmentioned in connection with the description of the compounds of theformula (I-a) according to the invention as being preferred or as beingparticularly preferred for R⁴. X preferably represents chlorine.

The sulphonyl halides of the formula (III) are known or can be preparedby known processes (J. Heterocyclic Chem. 1981, 997-1006).

Suitable diluents for carrying out the process according to theinvention are all inert organic solvents. Preference is given to usingaliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether,hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene,xylene or decalin; halogenated hydrocarbons, such as chlorobenzene,dichlorbenzene, dichloromethane, chloroform, tetrachloromethane,dichloroethane or trichloroethane; ethers, such as diethyl ether,diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane,tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole;ketones, such as acetone, butanone, methyl isobutyl ketone orcyclohexanone; nitriles, such as acetonitrile, propionitrile, n- ori-butyronitrile or benzonitrile; esters such as methyl acetate or ethylacetate.

Suitable acid binders for carrying out the process according to theinvention are all customary inorganic or organic bases. Preference isgiven to using alkaline earth metal or alkali metal hydrides,hydroxides, amides, alkoxides, acetates, carbonates or bicarbonates,such as sodium hydride, sodium amide, sodium methoxide, sodium ethoxide,potassium tert-butoxide, sodium hydroxide, potassium hydroxide, sodiumacetate, potassium acetate, calcium acetate, sodium carbonate, potassiumcarbonate, potassium bicarbonate or sodium bicarbonate, furthermoreammonium compounds, such as ammonium hydroxide, ammonium acetate orammonium carbonate, and also tertiary amines, such as trimethylamine,triethylamine, tributylamine, N,N-dimethylaniline,N,N-dimethylbenzylamine, pyridine, N-methylpiperidine,N-methylmorpholine, N,N-dimethylaminopyridine, diazabicyclooctane(DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).

When carrying out the process according to the invention, the reactiontemperatures can be varied within a relatively wide range. In general,the process is carried out at temperatures between 0° C. and 150° C.,preferably between 20° C. and 120° C.

For carrying out the process according to the invention, generally from1 to 2 mol, preferably from 1 to 1.3 mol, of the sulphonyl halide of theformula (III) and, if appropriate, from 1.0 to 2.0 mol, preferably from1.0 to 1.3 mol, of acid acceptor are employed per mole of oxadiazoloneof the formula (II).

The process according to the invention is generally carried out underatmospheric pressure. However, it is also possible to operate underelevated or reduced pressure--in general between 0.1 bar and 10 bar.

Work-up is carried out by customary methods.

The compounds which can be used according to the invention have potentmicrobicidal activity and can be employed for controlling undesirablemicroorganisms, such as fungi and bacteria, in crop protection and inthe protection of materials.

Fungicides are employed in crop protection for controllingPlasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes.

Bactericides are employed in crop protection for controllingPseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceaeand Streptomycetaceae.

Some pathogens causing fungal and bacterial diseases which come underthe generic names listed above are mentioned as examples, but not by wayof limitation:

Xanthomonas species, such as, for example, Xanthomonas campestris pv.oryzae;

Pseudomonas species, such as, for example, Pseudomonas syringae pv.lachrymans;

Erwinia species, such as, for example, Erwinia amylovora;

Pythium species, such as, for example, Pythium ultimum;

Phytophthora species, such as, for example, Phytophthora infestans;

Pseudoperonospora species, such as, for example, Pseudoperonosporahumuli or Pseudoperonospora cubensis;

Plasmopara species, such as, for example, Plasmopara viticola;

Bremia species, such as, for example, Bremia lactucae,

Peronospora species, such as, for example, Peronospora pisi or P.brassicae;

Erysiphe species, such as, for example, Erysiphe graminis;

Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;

Podosphaera species, such as, for example, Podosphaera leucotricha;

Venturia species, such as, for example, Venturia inaequalis;

Pyrenophora species, such as, for example, Pyrenophora teres or P.graminea (conidia form: Drechslera, syn: Helminthosporium);

Cochliobolus species, such as, for example, Cochliobolus sativus(conidia form: Drechslera, syn: Helminthosporium);

Uromyces species, such as, for example, Uromyces appendiculatus;

Puccinia species, such as, for example, Puccinia recondita;

Sclerotinia species, such as, for example, Sclerotinia sclerotiorum;

Tilletia species, such as, for example, Tilletia caries;

Ustilago species, such as, for example, Ustilago nuda or Ustilagoavenae;

Pellicularia species, such as, for example, Pellicularia sasakii;

Pyricularia species, such as, for example, Pyricularia oryzae;

Fusarium species, such as, for example, Fusarium culmorum;

Botrytis species, such as, for example, Botrytis cinerea;

Septoria species, such as, for example, Septoria nodorum;

Leptosphaeria species, such as, for example, Leptosphaeria nodorum;

Cercospora species, such as, for example, Cercospora canescens;

Alternaria species, such as, for example, Alternaria brassicae;

Pseudocercosporella species, such as, for example, Pseudocercosporellaherpotrichoides.

The fact that the active compounds are well tolerated by plants at theconcentrations required for controlling plant diseases permits thetreatment of aerial parts of plants, of propagation stock and seeds, andof the soil.

The active compounds which can be used according to the invention can beemployed particularly successfully for controlling diseases in fruit andvegetable growing and viticulture, such as, for example, againstPhytophthora and Plasmopara species. They are also very successfullyused for controlling cereal diseases, such as, for example,Leptosphaeria or Pyrenophora species, and also rice diseases, such as,for example, Pyricularia species.

Furthermore, the compounds which can be used according to the inventionare also suitable for increasing the yield of crops. Moreover, they havereduced toxicity and they are well-tolerated by plants.

In the protection of materials, the compounds which can be usedaccording to the invention can be employed for protecting industrialmaterials against infection with, and destruction by, undesiredmicroorganisms.

Industrial materials in the present context are understood as meaningnon-living materials which have been prepared for use in industry. Forexample, industrial materials which are intended to be protected byactive compounds according to the invention from microbial change ordestruction can be adhesives, sizes, paper and board, textiles, leather,wood, paints and plastic articles, cooling lubricants and othermaterials which can be infected with, or destroyed by, microorganisms.Parts of production plants, for example cooling-water circuits, whichmay be impaired by the proliferation of microorganisms may also bementioned within the scope of the materials to be protected. Industrialmaterials which may be mentioned within the scope of the presentinvention are preferably adhesives, sizes, paper and board, leather,wood, paints, cooling lubricants and heat-transfer liquids, particularlypreferably wood.

Microorganisms capable of degrading or changing the industrial materialswhich may be mentioned are, for example, bacteria, fungi, yeasts, algaeand slime organisms. The active compounds according to the inventionpreferably act against fungi, in particular moulds, wood-discolouringand wood-destroying fungi (Basidiomycetes), and against slime organismsand algae.

Microorganisms of the following genera may be mentioned as examples:

Alternaria, such as Alternaria tenuis,

Aspergillus, such as Aspergillus niger,

Chaetomium, such as Chaetomium globosum,

Coniophora, such as Coniophora puetana,

Lentinus, such as Lentinus tigrinus,

Penicillium, such as Penicillium glaucum,

Polyporus, such as Polyporus versicolor,

Aureobasidium, such as Aureobasidium pullulans,

Sclerophoma, such as Sclerophoma pityophila,

Trichoderma, such as Trichoderma viride,

Escherichia, such as Escherichia coli,

Pseudomonas, such as Pseudomonas aeruginosa, and

Staphylococcus, such as Staphylococcus aureus.

Depending on their particular physical and/or chemical properties, theactive compounds can be converted to the customary formulations, such assolutions, emulsions, suspensions, powders, foams, pastes, granules,aerosols and microencapsulations in polymeric substances and in coatingcompositions for seeds, and ULV cool and warm fogging formulations.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, liquefiedgases under pressure, and/or solid carriers, optionally with the use ofsurfactants, that is emulsifiers and/or dispersants, and/or foamformers. In the case of the use of water as an extender, organicsolvents can, for example, also be used as auxiliary solvents. Thefollowing are mainly suitable as liquid solvents: aromatics such asxylene, toluene or alkylnaphthalenes, chlorinated aromatics orchlorinated aliphatic hydrocarbons such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons such ascyclohexane or paraffins, for example petroleum fractions, alcohols suchas butanol or glycol and their ethers and esters, ketones such asacetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone,strongly polar solvents such as dimethylformamide or dimethylsulphoxide, or else water. Liquefied gaseous extenders or carriers areto be understood as meaning liquids which are gaseous at standardtemperature and under atmospheric pressure, for example aerosolpropellants such as halogenated hydrocarbons, or else butane, propane,nitrogen and carbon dioxide. Suitable solid carriers are: for exampleground natural minerals such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals such as highly disperse silica, alumina and silicates. Suitablesolid carriers for granules are: for example crushed and fractionatednatural rocks such as calcite, marble, pumice, sepiolite and dolomite,or else synthetic granules of inorganic and organic meals, and granulesof organic material such as sawdust, coconut shells, maize cobs andtobacco stalks. Suitable emulsifiers and/or foam formers are: forexample nonionic and anionic emulsifiers, such as polyoxyethylene fattyacid esters, polyoxyethylene fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates,or else protein hydrolysates. Suitable dispersants are: for examplelignin-sulphite waste liquors and methylcellulose.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, or else naturalphospholipids such as cephalins and lecithins and syntheticphospholipids can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs suchas alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs,and trace nutrients such as salts of iron, manganese, boron, copper,cobalt, molybdenum and zinc.

The formulations generally comprise between 0.1 and 95 per cent byweight of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be used as such orin their formulations also mixed with known fungicides, bactericides,acaricides, nematicides or insecticides in order thus, for example, towiden the spectrum of action or to prevent development of resistance. Inmany cases, synergistic effects are achieved, i.e. the activity of themixture exceeds the activity of the individual components.

Examples of co-components in mixtures are the following compounds:

Fungicides

aldimorph, ampropylfos, ampropylfos potassium, andoprim, anilazine,azaconazole, azoxystrobin,

benalaxyl, benodanil, benomyl, benzamacril, benzamacril-isobutyl,bialaphos, binapacryl, biphenyl, bitertanol, blasticidin-S,bromuconazole, bupirimate, buthiobate,

calcium polysulphide, capsimycin, captafol, captan, carbendazim,carboxin, carvon, quinomethionate, chlobenthiazone, chlorfenazole,chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon,cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuram,

debacarb, dichlorophen, diclobutrazole, diclofluanid, diclomezine,dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph,diniconazole, diniconazole-M, dinocap, diphenylamine, dipyrithione,ditalimfos, dithianon, dodemorph, dodine, drazoxolon,

ediphenphos, epoxiconazole, etaconazole, ethirimol, etridiazole,

famoxadon, fenapanil, fenarimol, fenbuconazole, fenfuram, fenitropan,fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentinhydroxide, ferbam, ferimzone, fluazinam, flumetover, fluoromide,fluquinconazole, flurprimidol, flusilazole, flusulphamide, flutolanil,flutriafol, folpet, fosetyl-aluminium, fosetyl-sodium, fthalide,fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole,furconazole-cis, furmecyclox,

guazatine,

hexachlorobenzene, hexaconazole, hymexazole,

imazalil, imibenconazole, iminoctadine, iminoctadine albesilate,iminoctadine triacetate, iodocarb, ipconazole, iprobenfos (IBP),iprodione, irumamycin, isoprothiolane, isovaledione,

kasugamycin, kresoxim-methyl, copper preparations, such as: copperhydroxide, copper naphthenate, copper oxychloride, copper sulphate,copper oxide, oxine-copper and Bordeaux mixture,

mancopper, mancozeb, maneb, meferimzone, mepanipyrim, mepronil,metalaxyl, metconazole, methasulphocarb, methfuroxam, metiram,metomeclam, metsulphovax, mildiomycin, myclobutanil, myclozolin,

nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol,

ofurace, oxadixyl, oxamocarb, oxolinic acid, oxycarboxim, oxyfenthiin,

paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen,pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz,procymidone, propamocarb, propanosine-sodium, propiconazole, propineb,pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur,

quinconazole, quintozene (PCNB),

sulphur and sulphur preparations,

tebuconazole, tecloftalam, tecnazene, tetcyclacis, tetraconazole,thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram,tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol,triazbutil, triazoxide, trichlamide, tricyclazole, tridemorph,triflumizole, triforine, triticonazole,

uniconazole,

validamycin A, vinclozolin, viniconazole,

zarilamide, zineb, ziram and also

Dagger G,

OK-8705,

OK-8801,

α-(1,1-dimethylethyl)-β-(2-phenoxyethyl)-1H-1,2,4-triazole-1-ethanol,

α-(2,4-dichlorophenyl)-β-fluoro-β-propyl-1H-1,2,4-triazole-1-ethanol,

α-(2,4-dichlorophenyl)-β-methoxy-α-methyl-1H-1,2,4-triazole-1-ethanol,

α-(5-methyl-1,3-dioxan-5-yl)-β-[[4-(trifluoromethyl)-phenyl]-methylene]-1H-1,2,4-triazole-1-ethanol,

(5RS,6RS)-6-hydroxy-2,2,7,7-tetramethyl-5-(1H-1,2,4-triazol-1-yl)-3-octanone,

(E)-a-(methoxyimino)-N-methyl-2-phenoxy-phenylacetamide,

isopropyl{2-methyl-1-[[[1-(4-methylphenyl)-ethyl]-amino]-carbonyl]-propyl}-carbamate,

1-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)ethanone-O-(phenylmethyl)-oxime,

1-(2-methyl-1-naphthalenyl)-1H-pyrrol-2,5-dione,

1-(3,5-dichlorophenyl)-3-(2-propenyl)-2,5-pyrrolidindione,

1-[(diiodomethyl)-sulphonyl]-4-methyl-benzene,

1-[[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl]-methyl]-1H-imidazole,

1-[[2-(4-chlorophenyl)-3-phenyloxiranyl]-methyl]-1H-1,2,4-triazole,

1-[1-[2-[(2,4-dichlorophenyl)-methoxy]-phenyl]-ethenyl]-1H-imidazole,

1-methyl-5-nonyl-2-(phenylmethyl)-3-pyrrolidinole,

2',6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoro-methyl-1,3-thiazole-5-carboxanilide,

2,2-dichloro-N-[1-(4-chlorophenyl)-ethyl]-1-ethyl-3-methyl-cyclopropanecarboxamide,

2,6-dichloro-5-(methylthio)-4-pyrimidinyl-thiocyanate,

2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide,

2,6-dichloro-N-[[4-(trifluoromethyl)-phenyl]-methyl]-benzamide,

2-(2,3,3-triiodo-2-propenyl)-2H-tetrazole,

2-[(1-methylethyl)sulphonyl]-5-(trichloromethyl)-1,3,4-thiadiazole,

2-[[6-deoxy-4-O-(4-O-methyl-β-D-glycopyranosyl)-a-D-glucopyranosyl]-amino]-4-methoxy-1H-pyrrolo[2,3-d]pyrimidine-5-carbonitrile,

2-aminobutane,

2-bromo-2-(bromomethyl)-pentanedinitrile,

2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecarboxamide,

2-chloro-N-(2,6-dimethylphenyl)-N-(isothiocyanatomethyl)-acetamide,

2-phenylphenol (OPP),

3,4-dichloro-1-[4-(difluoromethoxy)-phenyl]-1H-pyrrol-2,5-dione,

3,5-dichloro-N-[cyano[(1-methyl-2-propynyl)-oxy]-methyl]-benzamide,

3-(1,1-dimethylpropyl-1-oxo-1H-indene-2-carbonitrile,

3-[2-(4-chlorophenyl)-5-ethoxy-3-isoxazolidinyl]-pyridine,

4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulphonamide,

4-methyl-tetrazolo[1,5-a]quinazolin-5(4H)-one,

8-(1,1-dimethylethyl)-N-ethyl-N-propyl-1,4-dioxaspiro[4.5]decane-2-methanamine,

8-hydroxyquinoline sulphate,

9H-xanthene-2-[(phenylamino)-carbonyl]-9-carboxylic hydrazide,

bis-(1-methylethyl)-3-methyl-4-[(3-methylbenzoyl)-oxy]-2,5-thiophenedicarboxylate,

cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol,

cis-4-[3-[4-(1,1-dimethylpropyl)-phenyl-2-methylpropyl]-2,6-dimethylmorpholinehydrochloride,

ethyl [(4-chlorophenyl)-azo]-cyanoacetate,

potassium hydrogen carbonate,

methanetetrathiol sodium salt,

methyl1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate,

methyl N-(2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninate,

methyl N-(chloroacetyl)-N-(2,6-dimethylphenyl)-DL-alaninate,

N-(2,3-dichloro-4-hydroxyphenyl)-1-methyl-cyclohexanecarboxamide.

N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-furanyl)-acetamide,

N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-thienyl)-acetamide,

N-(2-chloro-4-nitrophenyl)-4-methyl-3-nitro-benzenesulphonamide,

N-(4-cyclohexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidinamine,

N-(4-hexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidinamine,

N-(5-chloro-2-methylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)-acetamide,

N-(6-methoxy)-3-pyridinyl)-cyclopropanecarboxamide,

N-[2,2,2-trichloro-1-[(chloroacetyl)-amino]-ethyl]-benzamide,

N-[3-chloro-4,5-bis-(2-propinyloxy)-phenyl]-N'-methoxy-methanimidamide,

N-formyl-N-hydroxy-DL-alanine sodium salt,

O,O-diethyl [2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate,

O-methyl S-phenyl phenylpropylphosphoramidothioate,

S-methyl 1,2,3-benzothiadiazole-7-carbothioate,

spiro[2H]-1-benzopyran-2,1'(3'H)-isobenzofuran]-3'-one,

Bactericides

bromopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin,probenazole, streptomycin, tecloftalam, copper sulphate and other copperpreparations.

Insecticides/Acaricides/Nematicides

abamectin, acephate, acrinathrin, alanycarb, aldicarb, alphamethrin,amitraz, avermectin, AZ 60541, azadirachtin, azinphos A, azinphos M,azocyclotin,

Bacillus thuringiensis,4-bromo-2-(4-chlorophenyl)-1-(ethoxymethyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile,bendiocarb, benfuracarb, bensultap, betacyfluthrin, bifenthrin, BPMC,brofenprox, bromophos A, bufencarb, buprofezin, butocarboxim,butylpyridaben,

cadusafos, carbaryl, carbofuran, carbophenothion, carbosulphan, cartap,chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos,chlorfluazuron, chlormephos,N-[(6-chloro-3-pyridinyl)-methyl]-N-cyano-N-methyl-ethanimidamide,chlorpyrifos, chlorpyrifos M, cis-resmethrin, clocythrin, clofentezine,cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin,cypermethrin, cyromazine,

deltamethrin, demeton M, demeton S, demeton S-methyl, diafenthiuron,diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion,diflubenzuron, dimethoate,

dimethylvinphos, dioxathion, disulphoton, edifenphos, emamectin,esfenvalerate, ethiofencarb, ethion, ethofenprox, ethoprophos,etrimphos,

fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb,fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate,fenthion, fenvalerate, fipronil, fluazinam, fluazuron, flucycloxuron,flucythrinate, flufenoxuron, flufenprox, fluvalinate, fonophos,formothion, fosthiazate, fubfenprox, furathiocarb,

HCH, heptenophos, hexaflumuron, hexythiazox,

imidacloprid, iprobenfos, isazophos, isofenphos, isoprocarb, isoxathion,ivermectin,

lambda-cyhalothrin, lufenuron,

malathion, mecarbam, mevinphos, mesulphenphos, metaldehyde, methacrifos,methamidophos, methidathion, methiocarb, methomyl, metolcarb,milbemectin, monocrotophos, moxidectin,

naled, NC 184, nitenpyram,

omethoate, oxamyl, oxydemethon M, oxydeprofos,

parathion A, parathion M, permethrin, phenthoate, phorate, phosalone,phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M, pirimiphos A,profenofos, promecarb, propaphos, propoxur, prothiophos, prothoate,pymetrozin, pyrachlophos, pyridaphenthion, pyresmethrin, pyrethrum,pyridaben, pyrimidifen, pyriproxifen,

quinalphos,

salithion, sebufos, silafluofen, sulphotep, sulprofos,

tebufenozide, tebufenpyrad, tebupirimiphos, teflubenzuron, tefluthrin,temephos, terbam, terbufos, tetrachlorvinphos, thiafenox, thiodicarb,thiofanox, thiomethon, thionazin, thuringiensin, tralomethrin,triarathen, triazophos, triazuron, trichlorfon, triflumuron,trimethacarb,

vamidothion, XMC, xylylcarb, zetamethrin.

It is also possible to admix other known active compounds, such asherbicides, fertilizers and growth-promoting substances.

The active compounds can be used as such, in the form of theirformulations or the use forms prepared therefrom, such as ready-to-usesolutions, suspensions, wettable powders, pastes, soluble powders, dustsand granules. They are used in the customary manner, for example bypouring, spraying, atomizing, spreading, dusting, foaming, brushing onand the like. It is further possible to apply the active compounds bythe ultra-low volume method or to inject the active compoundformulation, or the active compound itself, into the soil. The seed ofthe plants can also be treated.

When the active compounds which can be used according to the inventionare employed as fungicides, the application rates can be varied within arelatively wide range, depending on the form of application. In thetreatment of parts of plants, the active compound application rates inthe use forms are, in general, between 0.1 and 10,000 g/ha, preferablybetween 10 and 1000 g/ha. In the treatment of seed, application ratesactive compound of from 0.001 to 50 g, preferably 0.01 to 10 g, aregenerally required per kilogram of seed. In the treatment of the soil,active compound application rates of between 0.1 and 10,000 g/ha,preferably between 1 and 5000 g/ha, are employed.

The compositions used for the protection of industrial materialsgenerally comprise an amount of 1 to 95% by weight, preferably 10 to 75%by weight, of the active compounds.

The use concentrations of the active compounds which can be usedaccording to the invention depend on the species and the occurrence ofthe microorganisms to be controlled and on the composition of thematerial to be protected. The optimal rate of application can bedetermined by test series. In general, the use concentrations are in therange from 0.001 to 5% by weight, preferably 0.05 to 1.0% by weight,based on the material to be protected.

The activity and the activity spectrum of the active compounds to beused according to the invention in the protection of materials, or ofthe compositions, concentrates or quite generally formulations which canbe prepared therefrom, can be increased by adding, if appropriate, otherantimicrobially active compounds, fungicides, bactericides, herbicides,insecticides or other active compounds to widen the activity spectrum orto obtain particular effects, such as, for example, the additionalprotection against insects. These mixtures may have a broader activityspectrum than the compounds according to the invention.

The preparation and the use of active compounds which can be usedaccording to the invention are illustrated by the examples below.

PREPARATION EXAMPLES

Example 1 ##STR33##

At room temperature, a mixture of 2.0 g (15 mmol) of3-phenyl-4H-[1,2,4]oxadiazol-5-one and 30 ml absolute tetrahydrofuran isadmixed with stirring with 0.40 g (10 mmol) of a suspension of sodiumhydride (60% strength) and then stirred at room temperature for 10minutes. 1.9 g (10 mmol) of 3,5-dimethylisoxazol-4-sulphonyl chlorideare subsequently added, and the mixture is stirred at room temperaturefor another 20 hours. For work-up, the reaction mixture is poured into150 ml of water. The resulting mixture is extracted twice with 80 ml ofethyl acetate each time. The combined organic phases are dried oversodium sulphate and concentrated under reduced pressure. The residuethat remains is chromatographed over silica gel using methylene chlorideas mobile phase. In this manner, 0.3 g (9% of theory) of4-(3,5-dimethylisoxazole-4-sulphonyl)-3-phenyl-4H-[1,2,4]oxadiazol-5-oneis obtained in the form of a colourless solid of melting point 90 to 95C.

Example 2 ##STR34##

At room temperature, a mixture of 1.7 g (10 mmol) of3-thiophen-2-yl-4H-[1,2,4]oxadiazol-5-one and 30 ml of absoluteacetonitrile is admixed with stirring with 2.3 g (17 mmol) of powderedpotassium carbonate. 1.0 g (5.5 mmol) 2.0 g (10 mmol) of3,5-dimethylisoxazole-4-sulphonyl chloride are subsequently added, andthe mixture is stirred at room temperature for another 20 hours. Forwork-up, the reaction mixture is poured into 150 ml of water. Theresulting solid is filtered off, washed first with 10 ml of water andsubsequently with 20 ml of diethyl ether and dried. This gives 1.77 g(57% of theory) of4-(3,5-dimethylisoxazole-4-sulphonyl)-3-thiophen-2-yl-4H-[1,2,4]oxadiazol-5-onein the form of a yellow solid of melting point 138 C.

The sulphonyloxadiazolones of the formula (I) listed in Table 14 beloware also prepared by the methods given above.

                                      TABLE 14                                    __________________________________________________________________________                                                  (I)                              ##STR35##                                                                    Ex.                                                                           No.                                                                              R.sup.1      A            R.sup.2      M(° C.)                      __________________________________________________________________________    3  phenyl       --           --NMe.sub.2  92-96                               4  3-chlorophenyl                                                                             --                                                                                          ##STR36##   160-164                             5  3-chlorophenyl                                                                             --           --NMe.sub.2   97-101                             6  2-chlorophenyl                                                                             --                                                                                          ##STR37##   150-155                             7  4-chlorophenyl                                                                             --                                                                                          ##STR38##   155-156                             8  4-chlorophenyl                                                                             --                                                                                          ##STR39##   203-204                             9  phenyl       --                                                                                          ##STR40##   193-194                             10 2,4-dichlorophenyl                                                                         --                                                                                          ##STR41##   155-156                             11 phenyl       --           --CH.sub.3   149-151                             12 phenyl       --           2-methyl-5-nitrophenyl                                                                     170-171                             13 phenyl       --                                                                                          ##STR42##   132-133                             14 4-chlorophenyl                                                                             --           2-methyl-5-nitrophenyl                                                                     157-159                             15 4-chlorophenyl                                                                             --                                                                                          ##STR43##   146-147                             16 3-chlorophenyl                                                                             --                                                                                          ##STR44##   142-143                             17 3-chlorophenyl                                                                             --                                                                                          ##STR45##   153-154                             18 3,4-dichlorophenyl                                                                         --                                                                                          ##STR46##   147-148                             19 3,4-dichlorophenyl                                                                         --                                                                                          ##STR47##   196-198                             20 4-chloro-2-methylphenyl                                                                    --                                                                                          ##STR48##   169-170                             21 4-chloro-2-methylphenyl                                                                    --           --NMe.sub.2  128-129                             22 4-chloro-2-methylphenyl                                                                    --                                                                                          ##STR49##   165-166                             23 4-chlorophenyl                                                                             --                                                                                          ##STR50##   148-149                             24 phenyl       --                                                                                          ##STR51##   159-160                             25 phenyl       --                                                                                          ##STR52##   132-133                             26 3-tolyl      --                                                                                          ##STR53##   110-111                             27 3-tolyl      --                                                                                          ##STR54##   151-152                             28 2-tolyl      --                                                                                          ##STR55##   124-125                             29 2-tolyl      --           --NMe.sub.2  91-93                               30 2-tolyl      --                                                                                          ##STR56##   159-160                             31 2-thienyl    --                                                                                          ##STR57##   185-186                             32 4-tolyl      --                                                                                          ##STR58##   146-148                             33 4-trifluoromethyl-  phenyl                                                                 --                                                                                          ##STR59##   157-158                             34 phenyl       --CH.sub.2 --                                                                               ##STR60##   114-115                             35                                                                                ##STR61##   --                                                                                          ##STR62##   132-134                             36 2-pyridyl    --                                                                                          ##STR63##   134-135                             37 H                                                                                           ##STR64##                                                                                  ##STR65##   178-180                             38                                                                                ##STR66##   --                                                                                          ##STR67##   190-191                             39 2-pyridyl    --                                                                                          ##STR68##   187-189                             40 H                                                                                           ##STR69##                                                                                  ##STR70##   130-132                             41 4-tolyl      --                                                                                          ##STR71##   168-169                             42 4-trifluoromethyl-  phenyl                                                                 --                                                                                          ##STR72##   176-180                             43 phenyl       --CH.sub.2 --                                                                               ##STR73##   153-155                             44                                                                                ##STR74##   --           2-methyl-5-nitrophenyl                                                                     185-188                             45 2-pyridyl    --           2-methyl-5-nitrophenyl                                                                     183-185                             46 H                                                                                           ##STR75##   2-methyl-5-nitrophenyl                                                                     181-182                             47 4-tolyl      --           2-methyl-5-nitrophenyl                                                                     159-160                             48 3-tolyl      --           2-methyl-5-nitrophenyl                                                                     149-151                             49 2-tolyl      --           2-methyl-5-nitrophenyl                                                                     153-155                             50 2-thienyl    --           2-methyl-5-nitrophenyl                                                                     178-180                             51 4-trifluoromethyl-                                                                         --           2-methyl-5-nitrophenyl                                                                     127-129                                phenyl                                                                     52 phenyl       --CH.sub.2 --                                                                              2-methyl-5-nitrophenyl                                                                     145-146                             53 4-methoxyphenyl                                                                            --CH.sub.2 --                                                                               ##STR76##   120-121                             54 4-methoxyphenyl                                                                            --CH.sub.2 --                                                                               ##STR77##   137-138                             55 4-methoxyphenyl                                                                            --CH.sub.2 --                                                                              2-methyl-5-nitrophenyl                                                                     155-156                             56 4-chlorophenyl                                                                             --           2-thienyl    141-142                             57 phenyl       --           2-thienyl    155-156                             58 4-tolyl      --           2-thienyl    152-153                             59 2-tolyl      --           2-thienyl    107-108                             60 H                                                                                           ##STR78##   2-thienyl    88-91                               61 2-thienyl    --           2-thienyl    125-126                             62 4-chlorophenyl                                                                             --                                                                                          ##STR79##   161-162                             63 4-chlorophenyl                                                                             --                                                                                          ##STR80##   223-225                             64 phenyl       --                                                                                          ##STR81##   191-192                             65 4-tolyl      --                                                                                          ##STR82##   149-150                             66 2-tolyl      --                                                                                          ##STR83##   147-148                             67 phenyl       --CH.sub.2 --                                                                               ##STR84##   134-135                             68 phenyl       --CH.sub.2 --                                                                              2-thienyl    119-121                             69 H                                                                                           ##STR85##                                                                                  ##STR86##   104-105                             70 4-methoxyphenyl                                                                            --                                                                                          ##STR87##   161-162                             71 4-methoxyphenyl                                                                            --                                                                                          ##STR88##   217-219                             72 4-methoxyphenyl                                                                            --           2-methyl-5-nitrophenyl                                                                     158-160                             73 4-methoxyphenyl                                                                            --                                                                                          ##STR89##   134-136                             74 4-methoxyphenyl                                                                            --                                                                                          ##STR90##   161-162                             75 4-methoxyphenyl                                                                            --                                                                                          ##STR91##   217-219                             76 4-methoxyphenyl                                                                            --           2-methyl-5-nitrophenyl                                                                     158-160                             77 4-methoxyphenyl                                                                            --                                                                                          ##STR92##   134-136                             78 4-methoxyphenyl                                                                            --           2-thienyl    146-149                             79 2,5-dichlorophenyl                                                                         --                                                                                          ##STR93##   170-171                             80 2,5-dichlorophenyl                                                                         --           --NMe.sub.2  131-132                             81 2,5-dichlorophenyl                                                                         --                                                                                          ##STR94##   199-201                             82 4-tolyl      --                                                                                          ##STR95##   205-207                             83 phenyl       --CH.sub.2 --                                                                               ##STR96##   144-146                             84                                                                                ##STR97##   --                                                                                          ##STR98##   130-132                             85                                                                                ##STR99##   --                                                                                          ##STR100##  175-177                             86                                                                                ##STR101##  --           2-methyl-5-nitrophenyl                                                                     164-166                             87 2,4-dichlorophenyl                                                                         --                                                                                          ##STR102##  162-163                             88 2,4-dichlorophenyl                                                                         --                                                                                          ##STR103##  184-186                             89 2-chlorophenyl                                                                             --                                                                                          ##STR104##  171-172                             90 2-trifluoromethylphenyl                                                                    --                                                                                          ##STR105##  151-152                             91 2-trifluoromethylphenyl                                                                    --                                                                                          ##STR106##  153-155                             92 4-tolyl      --                                                                                          ##STR107##  156-158                             93                                                                                ##STR108##  --                                                                                          ##STR109##  222-225                             94 3-methoxyphenyl                                                                            --                                                                                          ##STR110##  147-149                             95 3-methoxyphenyl                                                                            --                                                                                          ##STR111##  171-172                             96 H                                                                                           ##STR112##                                                                                 ##STR113##  107-108                             97 H                                                                                           ##STR114##                                                                                 ##STR115##  182-183                             98 3-trifluoromethylphenyl                                                                    --                                                                                          ##STR116##  167-168                             99 3-trifluoromethylphenyl                                                                    --                                                                                          ##STR117##  165-167                             100                                                                              2-fluorophenyl                                                                             --                                                                                          ##STR118##  108-110                             101                                                                              2-fluorophenyl                                                                             --                                                                                          ##STR119##  153-154                             102                                                                              3-fluorophenyl                                                                             --                                                                                          ##STR120##  109-110                             103                                                                              3-fluorophenyl                                                                             --                                                                                          ##STR121##  169-170                             104                                                                              4-fluorophenyl                                                                             --                                                                                          ##STR122##  130-132                             105                                                                              4-fluorophenyl                                                                             --                                                                                          ##STR123##  204-206                             106                                                                              2-methoxyphenyl                                                                            --                                                                                          ##STR124##  169-170                             107                                                                              2-methoxyphenyl                                                                            --                                                                                          ##STR125##  195-197                             108                                                                              phenyl       --*O--CH.sub.2 --                                                                           ##STR126##  126-128                             109                                                                              phenyl       --*O--CH.sub.2 --                                                                           ##STR127##  169-171                             110                                                                              4-phenoxyphenyl                                                                            --                                                                                          ##STR128##  128-130                             111                                                                              4-phenoxyphenyl                                                                            --                                                                                          ##STR129##  182-184                             112                                                                              3-methoxyphenyl                                                                            --CH.sub.2 --                                                                               ##STR130##  121-122                             113                                                                              3-methoxyphenyl                                                                            --CH.sub.2 --                                                                               ##STR131##  115-116                             114                                                                              3-nitrophenyl                                                                              --                                                                                          ##STR132##  179-181                             115                                                                              3-nitrophenyl                                                                              --                                                                                          ##STR133##  191-193                             116                                                                              2-nitrophenyl                                                                              --                                                                                          ##STR134##  212-213                             117                                                                              2-nitrophenyl                                                                              --                                                                                          ##STR135##  195-196                             118                                                                              4-nitrophenyl                                                                              --                                                                                          ##STR136##  209-211                             119                                                                              4-nitrophenyl                                                                              --                                                                                          ##STR137##  230-231                             120                                                                              2-trifluoromethylphenyl                                                                    --                                                                                          ##STR138##  162-163                             121                                                                              2-trifluoromethylphenyl                                                                    --                                                                                          ##STR139##  164-165                             122                                                                              3-trifluoromethoxy-  phenyl                                                                --                                                                                          ##STR140##  145-146                             123                                                                              3-trifluoromethoxy-  phenyl                                                                --                                                                                          ##STR141##  133-135                             124                                                                              4-phenylphenyl                                                                             --                                                                                          ##STR142##  107-108                             125                                                                              4-phenylphenyl                                                                             --                                                                                          ##STR143##  103-104                             126                                                                              phenyl       --*NH--CO--CH.sub.2 --                                                                      ##STR144##  152-154                             127                                                                              phenyl       --*NH--CO--CH.sub.2 --                                                                      ##STR145##  196-197                             128                                                                              4-chlorophenyl                                                                             --*NH--CO--CH.sub.2 --                                                                      ##STR146##  167-169                             129                                                                              4-chlorophenyl                                                                             --*NH--CO--CH.sub.2 --                                                                      ##STR147##  188-190                             130                                                                              4-tolyl      --CH.sub.2 --                                                                               ##STR148##  129-130                             131                                                                              4-tolyl      --CH.sub.2 --                                                                               ##STR149##  153-155                             132                                                                              4-chlorophenyl                                                                             --CH.sub.2 --                                                                               ##STR150##  101-102                             133                                                                              4-chlorophenyl                                                                             --CH.sub.2 --                                                                               ##STR151##  149-150                             134                                                                              H            --*CH.sub.2 --O--CH.sub.2 --CH.sub.2 --                                                     ##STR152##  72-73                               135                                                                              H            --*CH.sub.2 --O--CH.sub.2 --CH.sub.2 --                                                     ##STR153##  94-96                               136                                                                              H            --*O--CH.sub.2 --CH.sub.2 --                                                                ##STR154##  logP = 0.67                         137                                                                              H            --*O--CH.sub.2 --CH.sub.2 --                                                                ##STR155##  logP = 1.09                         138                                                                              3-tolyl      --CH.sub.2 --                                                                               ##STR156##  114-115                             139                                                                              3-tolyl      --CH.sub.2 --                                                                               ##STR157##  127-128                             140                                                                              3-chlorophenyl                                                                             --CH.sub.2 --                                                                               ##STR158##  136-137                             141                                                                              3-chlorophenyl                                                                             --CH.sub.2 --                                                                               ##STR159##  151-152                             142                                                                              3,4-dichlorophenyl                                                                         --CH.sub.2 --                                                                               ##STR160##  138-139                             143                                                                              4-trifluoromethylphenyl                                                                    --CH.sub.2 --                                                                               ##STR161##  179-180                             144                                                                              2-tolyl      --*O--CH.sub.2 --                                                                          --NMe.sub.2  **)                                 145                                                                              2-chlorophenyl                                                                             --*O--CH.sub.2 --                                                                          --NMe.sub.2  logP = 3.03                         146                                                                              2-chloro-4-  --*O--CH.sub.2 --                                                                          --NMe.sub.2  logP = 3.68                            trifluoromethylphenyl                                                      __________________________________________________________________________     The atoms labelled with * are in each case attached to R.sup.1                **) The compound was characterized by the .sup.1 H NMR spectrum (300 MHz,     TMS). δ = 2.25 (s, 3H); 2.82 (s, 3H); 3.15 (s, 3H) ppm.            

In the Table 14 Me represents methyl.

The log P values were determined in accordance with EEC Directive 79/831Annex V,A8 using HPLC (gradient method, acetonitrile/0.1% aqueousphosphoric acid).

Use Examples

Example A

Phytophthora test (tomato)/protective

Solvent: 47 parts by weight of acetone

Emulsifier: 3 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the stated application rate. After thespray coating has dried on, the plants are inoculated with an aqueousspore suspension of Phytophthora infestans. The plants arc then placedin an incubation cabin at approximately 20 C. and 100% relativeatmospheric humidity.

Evaluation is carried out 3 days after the inoculation. 0% represents anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

Active compounds, application rates and test results are shown in thetable below.

                  TABLE A                                                         ______________________________________                                        Phytophthora test (tomato)/protective                                                               Active com-                                                                   pound appli-                                                                  cation rate                                                                              Efficacy                                     Active compound       in g/ha    in %                                         ______________________________________                                        According to the invention                                                     ##STR162##           50         94                                            ##STR163##           50         98                                            ##STR164##           50         97                                            ##STR165##           50         97                                            ##STR166##           50         93                                            ##STR167##           50         98                                            ##STR168##           50         99                                            ##STR169##           50         100                                           ##STR170##           50         100                                           ##STR171##           50         96                                            ##STR172##           50         95                                            ##STR173##           50         96                                            ##STR174##           50         99                                            ##STR175##           50         97                                            ##STR176##           50         97                                            ##STR177##           50         99                                            ##STR178##           50         99                                            ##STR179##           50         99                                            ##STR180##           50         99                                            ##STR181##           50         93                                            ##STR182##           50         96                                            ##STR183##           50         96                                            ##STR184##           50         94                                            ##STR185##           50         97                                            ##STR186##           50         94                                            ##STR187##           50         95                                            ##STR188##           50         98                                            ##STR189##           50         90                                            ##STR190##           50         96                                            ##STR191##           50         95                                            ##STR192##           50         97                                            ##STR193##           50         99                                            ##STR194##           50         94                                            ##STR195##           50         96                                            ##STR196##           50         90                                            ##STR197##           50         94                                            ##STR198##           50         96                                            ##STR199##           50         99                                            ##STR200##           50         98                                            ##STR201##           50         98                                            ##STR202##           50         94                                            ##STR203##           50         96                                            ##STR204##           50         93                                            ##STR205##           50         94                                            ##STR206##           50         100                                           ##STR207##           50         94                                            ##STR208##           50         94                                            ##STR209##           50         91                                            ##STR210##           50         99                                            ##STR211##           50         96                                            ##STR212##           50         96                                            ##STR213##           50         94                                            ##STR214##           50         99                                           ______________________________________                                    

Example B

Plasmopara test (grapevine)/protective

Solvent: 47 parts by weight of acetone

Emulsifier: 3 parts by weight alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the stated application rate. After thespray coating has dried on, the plants are inoculated with an aqueousspore suspension of Plasmopara viticola and then remain in an incubationcabin at approximately 20 C. and 100% relative atmospheric humidity for1 day. The plants are subsequently placed in a greenhouse atapproximately 21 C. and approximately 90% relative atmospheric humidityfor 5 days. The plants are then moistened and placed in an incubationcabin for 1 day.

Evaluation is carried out 6 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

Active compounds, application rates and test results are shown in thetable below.

                  TABLE B                                                         ______________________________________                                        Plasmopara test (grapevine)/protective                                                            Active compound                                                               application rate in                                                                        Efficacy                                     Active compound     g/ha         in %                                         ______________________________________                                        According to the invention                                                     ##STR215##         50           93                                            ##STR216##         50           97                                            ##STR217##         50           100                                           ##STR218##         50           99                                            ##STR219##         50           99                                           ______________________________________                                    

What is claimed is:
 1. A sulphonyloxadiazolone of the formula ##STR220##in which A represents a single bond or represents alkanediyl,alkenediyl, alkinediyl or a grouping --*O--CH₂ --, --*O--CH₂ --CH₂ --,--*CH₂ --O--, --*CH₂ --O--CH₂ --CH₂ --, --*CH₂ --S--, --*S--CH₂ --,##STR221## where the atom labeled by * is in each case attached to R¹and R³ represents hydrogen or an alkyl group,R¹ represents hydrogen, anoptionally substituted cycloalkyl group, an optionally substitutedcycloalkenyl group, an optionally substituted aryl group or anoptionally substituted heterocyclic group and R⁴ represents anoptionally substituted alkyl group, an optionally substituted alkenylgroup, a dialkylamino group, a nitro-substituted phenyl group which mayalso contain one or two further substituents, or represents optionally asubstituted heterocyclic group, provided that R⁴ does not representpropyl when A represents a direct bond and R¹ represents a2,4,6-trimethyl-phenyl group.
 2. A process for preparing asulphonyloxadiazolone of the formula (Ia) according to claim 1comprising reactingan oxadiazolone of the formula ##STR222## in which Aand R¹ are as defined in claim 1, with a sulphonyl halide of the formula

    R.sup.4 --SO.sub.2 --X                                     (III)

in which R⁴ is as defined in claim 1 and X represents halogen,optionallyin the presence of an acid binder and optionally, in the presence of adiluent.
 3. A microbicidal composition comprising a microbicidallyeffective amount of at least one sulphonyloxadiazolone of the formula(Ia) of claim 1, and an extender and/or surfactant.
 4. Asulphonyloxadiazolone according to claim 1 represented by the formula##STR223##
 5. A sulphonyloxadiazolone according to claim 1 representedby the formula
 6. A sulphonyloxadiazolone according to claim 1represented by the formula
 7. A method for controlling undesirablemicroorganisms comprising applying a microbicidally effective amount ofa sulphonyloxadiazolone of the formula in whichA represents a singlebond or represents a dialkyl group, a dialkenyl group, a dialkynyl groupor a grouping --*O--CH₂ --, --*O--CH₂ --CH₂ --, --*CH₂ --O--,--*CH₂--O--CH₂ --CH₂ --, --*CH₂ --S--, --*S--CH₂ --, ##STR224## where the atomlabelled by * is in each case attached to R¹ and R³ represents hydrogenor an alkyl group, R¹ represents hydrogen, an optionally substitutedcycloalkyl group, an optionally substituted cycloalkenyl group, anoptionally substituted aryl group or an optionally substitutedheterocyclic group and R² represents, in each case; an optionallysubstituted alkyl, alkenyl,dialkylamino, aryl or heterocyclic group,tothe undesirable microorganisms and/or their habitat.
 8. The method ofclaim 7 in which a sulphonyloxadiazolone of the formula (I) in whichArepresents a single bond or represents a dialkyl group having 1 to 4carbon atoms, a dialkenyl group having 2 to 4 carbon atoms, a dialkynylgroup having 2 to 4 carbon atoms or a grouping --*O--CH₂ --, --*O--CH₂--CH₂ --, --*CH₂ --, --*CH₂ --O--CH₂ --CH₂ --, --*CH₂ --S--, --*S--CH₂--, ##STR225## where the atom labeled by * is in each case attached toR¹, R³ represents hydrogen or an alkyl group having 1 to 4 carbon atoms,R¹ represents hydrogen, or a cycloalkyl group having 3 to 8 carbon atomsor a cycloalkenyl group having 3 to 8 carbon atoms, each of which isoptionally mono- to trisubstituted by identical or differentsubstituents selected from the group consisting of halogen and alkylhaving 1 to 3 carbon atoms, or R¹ represents an aryl radical having 6 to10 carbon atoms, where each of these radicals may be mono- totrisubstituted by identical or different substituents selected from thegroup consisting ofhalogen, nitro, carbamoyl; in each case,straight-chain or branched alkyl, alkoxy, alkylthio or alkylsulphonylhaving in each case 1 to 6 carbon atoms; in each case, straight-chain orbranched alkenyl or alkenyloxy having in each case 2 to 6 carbon atoms;in each case, straight-chain or branched halogenoalkyl, halogenoalkoxy,halogenoalkylthio or halogenoalkylsulphonyl having in each case 1 to 6carbon atoms and 1 to 5 identical or different halogen atoms; in eachcase, straight-chain or branched halogenoalkenyl or halogenoalkenyloxyhaving in each case 2 to 6 carbon atoms and 1 to 5 identical ordifferent halogen atoms; in each case, straight-chain or branchedalkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl,hydroximinoalkyl or alkoximinoalkyl having in each case 1 to 6 carbonatoms in the individual alkyl moieties; in each case, doubly attachedalkylene or dioxyalkylene having in each case 1 to 6 carbon atoms andbeing in each case optionally mono- to tetrasubstituted by identical ordifferent substituents selected from the group consisting of halogen,straight-chain or branched alkyl having from 1 to 4 carbon atoms andstraight-chain or branched halogenoalkyl having 1 to 4 carbon atoms and1 to 5 identical or different halogen atoms; cycloalkyl having 3 to 6carbon atoms; and aryl, aryloxy, arylthio, arylalkyl, arylalkyloxy,arylalkylthio, heterocyclic, heterocyclyloxy, heterocyclylthio,heterocyclylalkyl, heterocyclylalkyloxy or heterocyclylalkylthio, wherethese aromatic or heterocyclic radicals may be mono- to trisubstitutedby identical or different substituents from the group consisting ofhalogen, nitro, straight-chain or branched alkyl having 1 to 4 carbonatoms, straight-chain or branched halogenoalkyl having 1 to 4 carbonatoms and 1 to 5 identical or different halogen atoms, straight-chain orbranched alkoxy or alkylthio having 1 to 4 carbon atoms, andstraight-chain or branched halogenoalkoxy having 1 to 4 carbon atoms and1 to 9 identical or different halogen atoms, or R¹ represents anunsaturated heterocyclic radical having 5 or 6 ring members and 1 to 3heteroatoms which may optionally be mono- to trisubstituted by identicalor different substituents selected from the group consisting of halogen,nitro, amino, hydroxyl; in each case straight-chain or branched alkyl,alkoxy, alkylthio or alkylsulphonyl having in each case 1 to 6 carbonatoms; in each case straight-chain or branched alkenyl or alkenyloxyhaving in each case 2 to 6 carbon atoms; in each case straight-chain orbranched halogenoalkyl, halogenoalkoxy, halogenoalkylthio orhalogenoalkylsulphonyl having in each case 1 to 6 carbon atoms and 1 to13 identical or different halogen atoms; in each case straight-chain orbranched alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl,hydroximinoalkyl or alkoximinoalkyl having in each case 1 to 6 carbonatoms in the individual alkyl moieties; cycloalkyl having 3 to 6 carbonatoms; and aryl, aryloxy, arylthio, arylalkyl, arylalkyloxy,arylalkylthio, heterocyclic, heterocyclyloxy, heterocyclylthio,heterocyclylalkyl, heterocyclylalkyloxy or heterocyclylalkylthio, wherethese aromatic or heterocyclic radicals may be mono- to trisubstitutedby identical or different substituents selected from the groupconsisting of halogen, nitro, straight-chain or branched alkyl having 1to 4 carbon atoms, straight-chain or branched halogenoalkyl having 1 to4 carbon atoms and 1 to 9 identical or different halogen atoms,straight-chain or branched alkoxy or alkylthio having 1 to 4 carbonatoms, straight-chain or branched halogenoalkoxy or halogenoalkylthiohaving 1 to 4 carbon atoms and 1 to 9 identical or different halogenatoms, and R² represents an alkyl group having 1 to 4 carbon atoms, analkenyl group having 2 to 4 carbon atoms, a halogenoalkyl group havingin each case 1 to 4 carbon atoms and 1 to 5 identical or differenthalogen atoms, a halogenoalkenyl group having in each case 2 to 4 carbonatoms and 1 to 5 identical or different halogen atoms or representsdialkylamino having in each case 1 to 4 carbon atoms in the two alkylgroups, or R² represents an aryl group having 6 to 10 carbon atoms whichmay be mono- to trisubstituted by identical or different substituentsselected from the group consisting of nitro, halogen, alkyl having 1 to4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5identical or different halogen atoms, halogenoalkoxy having 1 to 4carbon atoms and 1 to 5 identical or different halogen atoms andhalogenoalkylthio having 1 to 4 carbon atoms and 1 to 5 identical ordifferent halogen atoms, or R² represents a heterocyclic radical having5 or 6 ring members and 1 to 3 heteroatoms, where this radical maycontain an oxo group and may be mono- to trisubstituted by identical ordifferent substituents selected from the group consisting of halogen,cyano, nitro, amino, hydroxyl, alkyl having 1 to 4 carbon atoms, alkoxyhaving 1 to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 to4 carbon atoms and 1 to 5 identical or different halogen atoms,alkylcarbonyl having 1 to 4 carbon atoms in the alkyl moiety,alkoxycarbonyl having 1 to 3 carbon atoms in the alkoxy moiety,carbamoyl, alkylaminocarbonyl having 1 to 4 carbon atoms in the alkylmoiety, dialkylaminocarbonyl having 1 to 4 carbon atoms in theindividual alkyl moieties, hydroximinoalkyl or alkoximinoalkyl having ineach case 1 to 4 carbon atoms in the individual alkyl moieties andcycloalkyl having 3 to 6 carbon atoms is used.